Lubricant additives

The design of lubricants to decrease friction and wear in machine components is an important way to increase the energy efficiency of mechanical systems while taking into account restrictive environmental requirements and technological advances. Lubricants are composed of base oil and additives designed for specific performance needs.

The use of first principles calculations based on density functional theory has been traditionally very scarce in tribology, especially in the field of lubricant additives. However a fully quantum-mechanical approach is very important to provide an accurate description of the interfacial properties and of the surface chemical processes involving additive molecules, since experimental probing of tribochemistry processes in real-time is still extremely challenging.

We demonstrate the crucial role of the microscopic phenomenon of metal passivation by showing that the friction reduction is connected to to the amount of elemental sulphur and phosphorus released at the iron interface by tribochemical reactions; and that sulphur especially reduces the friction of steel-on-steel by reducing the adhesion and shear strength of iron. We also provide a description of the organophosphite dissociation paths at the iron surface.

S- and P-based lubricant additives

Sulfur and phosphorus are key elements for the functionality of lubricant additives used in extreme pressure applications, such as synchronizer systems in cars. To understand their mechanism of action we combine first principles calculations and gas phase lubrication experiments.

The surface spectroscopy analysis performed in situ after the tribological test indicates that iron sulfide (phosphide) is formed by rubbing steel-on-steel in the presence of organo-sulfur (–phosphorus) molecules. We, thus, study the effects of elemental sulfur and phosphorus on the interfacial properties of iron by spin-polarized density functional theory calculations. The results show that both the elements are very effective in reducing the adhesion and shear strength of iron. Sulfur is predicted to be more effective than phosphorus, especially at high pressure. Gas phase lubrication experiments confirm these results, indicating that the friction coefficient of iron-sulphide is lower than that of iron-phosphide and both S and P dramatically reduce the friction of steel-on-steel. These results indicate that the release of elemental sulfur and phosphorus may be the key mechanism to controlling the tribological properties of the metal interface and elucidate that the underling microscopic phenomenon is metal passivation.
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Trimethyl-phosphite dissociative adsorption on iron

The reaction of trimethyl-phosphite, TMPi, with a clean Fe(110) surface has been investigated by ab initio calculations. The most stable configurations and energies are identified for both molecular and dissociative adsorption.

The calculated reaction energies indicate that dissociation is energetically more favorable than molecular adsorption and we provide a description of the dissociation path and the associated energy barrier. In situ XPS analysis of adsorbed TMPi on metallic iron confirmed molecular chemisorption and dissociation at high temperature. These results shed light on the mechanism of phosphorus release from organophosphites at the iron surface, which is important for the functionality of these phosphorus-based additives, included in lubricants for automotive applications.
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Tribochemistry of phosphorus additives

Organophosphorus compounds are common additives included in liquid lubricants for many applications, in particular automotive applications. Typically, organic phosphites function as friction-modifiers whereas phosphates as anti-wear additives.

While the antiwear action of phosphates is now well understood, the mechanism by which phosphites reduce friction is still not clear. Here we study the tribochemistry of both phosphites and phosphates using gas phase lubrication (GPL) and elucidate the microscopic mechanisms that lead to the better frictional properties of phosphites. In particular, by in situ spectroscopic analysis we show that the friction reduction is connected to the presence of iron phosphide, which is formed by tribochemical reactions involving phosphites. The functionality of elemental phosphorus in reducing the friction of iron-based interfaces is elucidated by first principle calculations. In particular, we show that the work of separation and shear strength of iron dramatically decrease by increasing the phosphorus concentration at the interface. These results suggest that the functionality of phosphites as friction modifiers may be related to the amount of elemental phosphorus that they can release at the tribological interface.
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